Studies on the oxidative N-demethylation of atropine, thebaine and oxycodone using a Fe^III-TAML catalyst

Iron(IV) or iron(V)? Heterolytic or free radical? Oxidation pathways of a TAML activator in acetonitrile at −40 °C

“…The most significant among these are the Fe III superoxo complex, Fe III O 2 made from iron(III) and KO 2 at -5 °C in MeCN [29], the Fe IV OFe IV μ-oxo dimer which is generated by O 2 from iron(III) in noncoordinating solvents such as CH 2 Cl 2 under ambient conditions [30] and the Fe V O complex produced using m-chloroperoxybenzoic acid (mCPBA) at -40 °C in MeCN [31]. TAML complexes are used as catalysts in synthetically valuable transformations using different oxidizing agents under various conditions [32][33][34][35][36]. As a rule, the synthetic reports are concluded by postulated reaction mechanisms, in which high oxidation states of iron, often Fe V , are proposed irrespective of the reaction conditions and the oxidizing agent used.…”

ElectrochemicalN-demethylation of tropane alkaloids

“…1 N-Demethylation of tropane alkaloids to their nortropane derivatives is a key step in the semi-synthesis of some important therapeutic agents. 2,3 For example, noratropine 5 is an intermediate for the synthesis of the bronchodilator ipratropium bromide 6, which is in the WHO's list of essential medicines. Under the brand name of Combivent, ipratropium bromide had world-wide sales of $850 million and $950 million in 2008 and 2009, respectively, and is among the top 200 pharmaceutical products either by retail sales or prescriptions in the United States, in the last decade.…”

Molecular Iron-Based Oxidants and Their Stoichiometric Reactions

“…Somewhat surprisingly, stoichiometric reactivity studies have revealed that [Fe V O(TAML)] À is only a mediocre oxidant in the oxidation of alkenes and alkanes, when compared to the analogous Fe(IV)oxo species [86,126]. Regardless, the Fe-TAML system and its derivatives (especially systems where the ligand is decorated with electron-withdrawing fluoride substituents) are effective catalysts in the nonselective oxidation of sulfides, hydrocarbons, and chlorinated aromatic compounds with H 2 O 2 [127][128][129] and in the selective N-dealkylation of tropane alkaloids [130,131]. A key feature of the Fe-TAML systems is that despite being extremely good catalase mimics ( …”